Scalable Accelerated Materials Discovery of Sustainable Polysaccharide-Based Hydrogels by Autonomous Experimentation and Collaborative Learning.

While some materials can be discovered and engineered using standalone self-driving workflows, coordinating multiple stakeholders and workflows toward a common goal could advance autonomous experimentation (AE) for accelerated materials discovery (AMD). Here, we describe a scalable AMD paradigm based on AE and "collaborative learning". Collaborative learning using a novel consensus Bayesian optimization (BO) model enabled the rapid discovery of mechanically optimized composite polysaccharide hydrogels.

Electric Fields in Polymeric Systems.

Polymer-based electronic devices are limited by slow transport and recombination of newly separated charges. Built-in electric fields, which arise from compositional gradients, are known to improve charge separation, directional charge transport, and to reduce recombination. Yet, the optimization of these fields through the rational design of polymeric materials is not prevalent.

Reaction-Type-Dependent Behavior of Redox-Hopping in MOFs─Does Charge Transport Have a Preferred Direction?

Redox hopping is the primary method of electron transport through redox-active metal-organic frameworks (MOFs). While redox hopping adequately supports the electrocatalytic application of MOFs, the fundamental understandings guiding the design of redox hopping MOFs remain nascent. In this study, we probe the rate of electron and hole transport through a singular MOF scaffold to determine whether the properties of the MOF promote the transport of one carrier over the other.

Gelation during Ring-Opening Reactions of Cellulosics with Cyclic Anhydrides: Phenomena and Mechanisms.

Cellulose esters are used in Food and Drug Administration-approved oral formulations, including in amorphous solid dispersions (ASDs). Some bear substituents with terminal carboxyl moieties (e.g.

Polarizable AMOEBA force field predicts thin and dense hydration layer around monosaccharides.

Polarizable force fields crucially enhance the modeling of macromolecules in polar media. Here, we present new parameters to model six common monosaccharides with the polarizable AMOEBA force field. These parameters yield a thinner, but denser, hydration layer than that previously reported.

Exploring the effects of cellulose sources on silver reduction and the bacterial removal of nanocellulose-based hydrogel beads.

With water access challenged, there is a need to develop efficient and sustainable alternatives for water purification. Here, cellulose nanofibrils (CNFs) isolated from three source materials (softwood, soybean hulls and oat straw) were compared for the generation of hydrogels beads, and compared as support and reducing agent for silver nanoparticles formation. The silver-functionalized hydrogel beads (Ag-CNFs) were characterized, and the surface energy and specific surface area were evaluated.

ω-Carboxyl terminated cellulose esters are effective crystallization inhibitors for challenging drugs.

Polymeric additives are widely used to delay drug crystallization from supersaturated solutions, which is critical for enhancing oral bioavailability by amorphous solid dispersion (ASD). The efficacy of these polymers relies on their capacity to inhibit nucleation and subsequent crystal growth. Drug nucleation is pivotal to crystallization; therefore, effective polymers are essential for suppressing nucleation from supersaturated solutions.

Octopus-Inspired Adhesives with Switchable Attachment to Challenging Underwater Surfaces.

Adhesives that excel in wet or underwater environments are critical for applications ranging from healthcare and underwater robotics to infrastructure repair. However, achieving strong attachment and controlled release on difficult substrates, such as those that are curved, rough, or located in diverse fluid environments, remains a major challenge. Here, an octopus-inspired adhesive with strong attachment and rapid release in challenging underwater environments is presented.

Programmable adhesion through triangular and hierarchical cuts in metamaterial adhesives.

Metamaterial design approaches, which integrate structural elements into material systems, enable the control of uncommon behaviours by decoupling local and global properties. Leveraging this conceptual framework, metamaterial adhesives incorporate nonlinear cut architectures into adhesive films to achieve unique combinations of adhesion capacity, release, and spatial tunability by controlling how cracks propagate forward and in reverse directions during separation. Here, metamaterial adhesive designs are explored with triangular cut features while integrating hierarchical and secondary cut patterns among primary nonlinear cuts.

Electrospun Lithium Porous Nanosorbent Fibers for Enhanced Lithium Adsorption and Sustainable Applications.

Electrospun nanosorbent fibers specifically designed for efficient lithium extraction were developed, exhibiting superior physicochemical properties. These fibers were fabricated using a polyacrylonitrile/dimethylformamide matrix, with viscosity and dynamic mechanical analysis showing that optimal interactions were achieved at lower contents of layered double hydroxide. This meticulous adjustment in formulation led to the creation of lithium porous nanosorbent fibers (Li-PNFs-1).

Regulating HS release from self-assembled peptide HS-donor conjugates using cysteine derivatives.

Self-assembled peptides provide a modular and diverse platform for drug delivery, and innovative delivery methods are needed for delivery of hydrogen sulfide (HS), an endogenous signaling molecule (gasotransmitter) with significant therapeutic potential. Of the available types of HS donors, peptide/protein HS donor conjugates (PHDCs) offer significant versatility. Here we discuss the design, synthesis, and in-depth study of a PHDC containing three covalently linked components: a thiol-triggered HS donor based on an -aroylthiooxime (SATO), a GFFF tetrapeptide, and a tetraethylene glycol (TEG) dendron.

Multiscale crack trapping for programmable adhesives.

The precise control of crack propagation at bonded interfaces is crucial for smart adhesives with advanced performance. However, previous studies have primarily concentrated on either microscale or macroscale crack propagation. Here, we present a hybrid adhesive that integrates microarchitectures and macroscopic nonlinear cut architectures for unparalleled adhesion control.

Stimuli-Responsive Polymers at the Interface with Biology.

There has been growing interest in polymeric systems that break down or undergo property changes in response to stimuli. Such polymers can play important roles in biological systems, where they can be used to control the release of therapeutics, modulate imaging signals, actuate movement, or direct the growth of cells. In this Perspective, after discussing the most important stimuli relevant to biological applications, we will present a selection of recent exciting developments.

NO- and HS- releasing nanomaterials: A crosstalk signaling pathway in cancer.

The gasotransmitters nitric oxide (NO) and hydrogen sulfide (HS) play important roles not only in maintaining physiological functions, but also in pathological conditions and events. Importantly, these molecules show a complex interplay in cancer biology, demonstrating both tumor-promoting and anti-tumor activities depending on their concentration, flux, and the environmental redox state. Additionally, various cell types respond differently to NO and HS.

Kinetics of Calcite Nucleation onto Sulfated Chitosan Derivatives and Implications for Water-Polysaccharide Interactions during Crystallization of Sparingly Soluble Salts.

Anionic macromolecules are found at sites of CaCO biomineralization in diverse organisms, but their roles in crystallization are not well-understood. We prepared a series of sulfated chitosan derivatives with varied positions and degrees of sulfation, DS(SO ), and measured calcite nucleation rate onto these materials. Fitting the classical nucleation theory model to the kinetic data reveals the interfacial free energy of the calcite-polysaccharide-solution system, γ, is lowest for nonsulfated controls and increases with DS(SO ).

6-Carboxycellulose Acetate Butyrate: Effectiveness as an Amorphous Solid Dispersion Polymer.

Amorphous solid dispersion (ASD) in a polymer matrix is a powerful method for enhancing the solubility and bioavailability of otherwise crystalline, poorly water-soluble drugs. 6-Carboxycellulose acetate butyrate (CCAB) is a relatively new commercial cellulose derivative that was introduced for use in waterborne coating applications. As CCAB is an amphiphilic, carboxyl-containing, high glass transition temperature () polymer, characteristics essential to excellent ASD polymer performance, we chose to explore its ASD potential.

Polymer Characterization by Size-Exclusion Chromatography with Multi-Angle Light Scattering (SEC-MALS): A Tutorial Review.

This tutorial review presents the theory and application of SEC-MALS with minimal equations and a focus on synthetic polymer characterization, serving as an entry point for polymer scientists who want to learn more about SEC-MALS. We discuss the principles of static light scattering, outline its capability to generate absolute weight-average molar mass values, and extend its application to SEC-MALS. Practical elements are emphasized, enabling researchers to appreciate how values for , and are determined in an SEC-MALS experiment and how experimental conditions and input values, such as the specific refractive index increment ( ), influence the results.

Selective cross-metathesis of cellobiose derivatives with amido-functionalized olefinic structures: A model study for synthesis of cellulosic diblock copolymers.

This work describes a model study for synthesis of cellulose-based block copolymers, investigating selective coupling of peracetyl β-d-cellobiose and perethyl β-d-cellobiose at their reducing-ends by olefin cross-metathesis (CM). Herein we explore suitable pairs of ω-alkenamides that permit selective, quantitative coupling by CM. Condensation reactions of hepta-O-acetyl-β-d-cellobiosylamine or hepta-O-ethyl-β-d-cellobiosylamine with acyl chlorides afforded the corresponding N-(β-d-cellobiosyl)-ω-alkenamide derivatives with an aromatic olefin or linear olefinic structures.

Synthesis and real-time characterization of self-healing, injectable, fast-gelling hydrogels based on alginate multi-reducing end polysaccharides (MREPs).

Polysaccharide-based hydrogels are promising for many biomedical applications including drug delivery, wound healing, and tissue engineering. We illustrate herein self-healing, injectable, fast-gelling hydrogels prepared from multi-reducing end polysaccharides, recently introduced by the Edgar group. Simple condensation of reducing ends from multi-reducing end alginate (M-Alg) with amines from polyethylene imine (PEI) in water affords a dynamic, hydrophilic polysaccharide network.

Progress and Challenges in Polystyrene Recycling and Upcycling.

Polystyrene is a staple plastic in the packaging and insulation market. Despite its good recyclability, the willingness of PS recycling remains low, largely due to the high recycling cost and limited profitability. This review examines the research progresses, gaps, and challenges in areas that affect the recycling costs, including but not limited to logistics, packaging design, and policymaking.

A renewably sourced, circular photopolymer resin for additive manufacturing.

The additive manufacturing of photopolymer resins by means of vat photopolymerization enables the rapid fabrication of bespoke 3D-printed parts. Advances in methodology have continually improved resolution and manufacturing speed, yet both the process design and resin technology have remained largely consistent since its inception in the 1980s. Liquid resin formulations, which are composed of reactive monomers and/or oligomers containing (meth)acrylates and epoxides, rapidly photopolymerize to create crosslinked polymer networks on exposure to a light stimulus in the presence of a photoinitiator.

Dextran Macroinitiator for Synthesis of Polysaccharide--Polypeptide Block Copolymers via NCA Ring-Opening Polymerization.

Synthesis of polysaccharide--polypeptide block copolymers represents an attractive goal because of their promising potential in delivery applications. Inspired by recent breakthroughs in -carboxyanhydride (NCA) ring-opening polymerization (ROP), we present an efficient approach for preparation of a dextran-based macroinitiator and the subsequent synthesis of dextran--polypeptides via NCA ROP. This is an original approach to creating and employing a native polysaccharide macroinitiator for block copolymer synthesis.

Enhancing Electrical Conductivity of Stretchable Liquid Metal-Silver Composites through Direct Ink Writing.

Structure-property-process relationships are a controlling factor in the performance of materials. This offers opportunities in emerging areas, such as stretchable conductors, to control process conditions during printing to enhance performance. Herein, by systematically tuning direct ink write (DIW) process parameters, the electrical conductivity of multiphase liquid metal (LM)-silver stretchable conductors is increased by a maximum of 400% to over 1.